Method of producing modified phenol aldehyde resin



Mama, 1, 1945 i Q v 2,374,814

IVIETHOD OF PRODUCING MODIFIED PHENOL ALDEHYDE RESIN Samuel S. Gutkin, Brooklyn, N. Y., assignor to Falkda Company, Carnegie, Pa., a corporation of Pennsylvania No Drawing Application August 14, 1943,

7 Serial No. 498,730

8 Claims. (Cl. 260-44) This invention relates to a specialized resinsation product which would be, if unmodified, of oils phenol-aldehyde alkyd product and relates the Resite or Bakelite, or full heat-hardenmore particularly to phenol-aldehyde alkyd ing and infusible sort, and includes the involveproducts the specific properties of which are dement of that initial'condensate in reactions and termined by a specialized modification in the semodifications conducted with such determining ries of stages by which the resinous product is and modifying reagents, and under such condimade. The application herein is a continuationtions that the fusibility and solubility of the rein-part of my application Serial No. 306,291, filed action batch is maintained throughout the proc- November 27, 1939, now Patent No, 2,329,045, and ess and in measure is retained in the final prodmy application Serial No. 435,752, filed March 10 uct while also retaining in the product funda- 1942., mental characteristics of the infusible phenol- Primarily the object of my invention is so to aldehyde condensates. This I do by effectively link the alkyd reactions to a phenol-aldehyde reacting the fundamentally infusible phenol-alcondensate of the infusible, Resite or Bakelite dehyde condensate with an unmodified polyhytype that there is obtained a resin possessing cerdric alcohol and then with a polybasic carboxylic tain inherent properties of phenol-aldehyde resacid without destroying the above noted desirins of that sort, such as the capacity to acquire able properties inherent in the infusible phenoldensity and gloss in a film, coupled in measure aldehyde resins.

with the alkyd properties of flexibility, durabil- Following this I modify the resultant resinous y, and susceptibility to modification; by so conproduct of condensation and partial esterificaducting the process by which the resin is protion with a cyclic monocarboxylic acid.

duced that fusibility or solubility is retained in As typical examples of aldehydes which may the reaction mass, or batch, during the formation be reacted with phenol to give the phenol-aldeof the resin without impairing in the product hyde condensate, I may name acetaldehyde, those characteristics of a full heat-hardening butyraldehyde, propylaldehyde, crotonaldehyde, resin which have been above noted. I and formaldehyde. As typical examples of un- The further and more specific object of my inmodified polyhydric alcohols usable in my process, vention and the feature in which the resin which I may give glycerine, triethylene glycol, diethylene is the subject matter hereof differs from the resin glycol, pentaerythritol, and sorbitol. As typical of p i cally cl im d in my ove o ed applicapolybasic carboxylic acids which may be used, I tion Serial No. 306,291 is to utilize as a modifying may give phthalic anhydride, maleic anhydride, component in ud d in th resin one of the malic acid, and fumaric acid. It may be stated matic monocarboxylic acids or a mixture of such generally that I may use in my process any aldeacids. By the term "aromatic monocarboxylic hyde, any unmodified polyhydric alcohol, and any a ids as herein d, I intend primarily t polyba'sic carboxylic acid of the sort found suittinguish from the fatty oil acids, all of which are bl in the alkyd resin art. straight chain acids having more than 10 carbon A typical of the aromatic monocarboxylic atoms in their Carbon i and also to acids which I use, I may give benzoic acid, ethylin i h rom h w r a y m n yli benzoic acid, methyl-benzoic acid, anthranilic ac s hav I10 mo than 10 Carbon atoms in 40 (amino-benzoic) acid, tropic acid, hydratropic their non-nuclear structure attached to the carid, phenyl-acetig acid, tolyl-acetic acid, sali- Y cylic acid, cinnamic acid, hydro-cinnamic acid,

The resinous products made in accordance with d i i i id,

my invention difier from those disclosed in my Exam 16 N0 1 above identified application Serial No. 306,291 by p being as a class somewhat softer and more soluble I mixed 300 grams of commercial (approxithan those other products, and by having greater mately 40%) formaldehyde and 221 grams of comadhesiveness. They differ slightly from ealih/mercial (approximately 100%) meta-para-cresol other, but have in common the properties of fil with at least 3.5 cc. sodium hydroxide catalyst in formation, adhesion, and strength. All are 5 a concentration of 250 milligrams per cc. This homogeneous products in that they exhibit no mixture was refluxed until the first sign of sepinherent tendency toward separation after their aration of water occurred. Such separation is for tion, indicated by clouding in a cooled sample, 'or Generally stated my invention includes the region, of the reaction mass; and may be obinitial formation of a phenol-aldehyde condenserved for instance in the cooled region of a or checking apparatus.

glass reaction flask forming part of experimental Upon the appearance or such ,cloud, and cooling the batch, an opaque mass of resinous" condensate formed, together with an appreciable quantity of free water.

It is to' be understood that both the metapara-cresol and the formaldehyde of this example are common commerical materials, the formaldehyde being approximately 40% by volume and the meta-para-cresol being of usual commercial purity.

Taking 50 grams of the condensate thus formed I washed it several times with water and removed as much water as possible by decantation and squeezing, in accordance with my preferred practice. Prior to any additional heating of the condensate I mixed with it 154 grams of highselected monocarboxylic acid 'to the reaction mass, or batch.

I have found that I may first heat to drive oil water from the homogeneous mass formed from the condensate and the glycerine and then add the polybasic carboxylic acid, or may add both the glycerine and the polybasic carboxylic acid before heating and then heat. The point is that in either case opportunity is given the glycerine as representative of the unmodified polyhydric alcohols so to interact with the condensate as to form a homogeneous fusible mass therewith before reaction with the polybasic carboxylic acid takes place, so that the product of reaction with the polybasic carboxylic acid remains clear and homogeneous.

The resultant product, if subjected to continued heating to a temperature higher than 320 F., is .a clear resinous material of plastic type, but less brittle than the simple phenol-formaldehyde condensate which forms its base. It is, however,

after reaction with the phthalic anhydride still susceptible to modification into products of fusible and soluble sort- It will be noted that to retain the fusibility of'this intermediate product the condensate content of which is fundamentally of the infusible type I utilize an unmodified polyhydric alcohol which is eifectlve to keep the condensate in soluble condition for reaction with the polybasic carboxylic acid.

In efiecting modification of the resinous material formed as above by effective esterification of the condensate and reaction with the phthalic anhydride, heating of the material is continued and held to the formatiofibf a clear bead. At that stage and without'perinitting the material to gel, I added 73 grams of benzoic acid with heating from .the maximunistemperature of the stage next preceding to a temperature of about 400 F.

With benzoic acid, as withthe other monocarboxylic acids of the class herein disclosed, a temperature of about 400 F. was adequate to incorous materialof straw color. It is indicated for use in adhesives, as a plasticizer for nitro-cellulose, and other cellulose materials, and when extended with suitable solvent, such as the aromatic hydrocarbon solvents, ester solvents, alcohols, ketones, catalytic solvents, or mixtures of such solvents, it is useful as a varnish coating.

As a variation under this same example, it may be noted that I have added as much as grams of benzoic acid, making the addition by small increments to avoid separation. It may be noted that in this example, and as a fact running through all the exemplifications of my method, that the greater the proportional addition of the monocarboxylic acid the less viscous will the product be, and the greater will be its solubility in the common organic solvents.

Example N0. 2

The procedure of thi example was identical with that of Example 'No. 1 and the materials used were identical with the materials of that example, except that 98 grams of maleic anhydride were used to replace the 148 grams of phthalic anhydride used in Example No. 1.

Example No. 3

The procedure of thi example was identical with that of Example No. land the materials used were identical with those of that example, except that 116 grams of fumaric acid were used instead of 148 grams of phthalic anhydride used in Example No. 1.

It should be noted that examples paralleling Examples Nos. 2 and 3 are not hereinafter given in conjunction with the use of other variable compounds within the bounds of my invention as herein broadly disclosed. It is, however, to be understood that in every subsequent example in which the use of phthalic anhydride is indicated, approximately an equivalent molar content 01' 'maleic anhydride, fumaric acid, or other polybasic carboxylic acid may be used equivalently to the phthalic anhydride as the polybasic carboxylic acid component of my resin, the procedure in each instance being identical with that 1 described when phthalic anhydride was used. I

have observed only slight differences between the products in which phthalic anhydride was used as the polybasic carboxylic acid and those products in which some other polybasic carboxylic acid was used.

Example No. 4

In this example the procedure and materials of Example No. 1 were duplicated down to the final stage, in which stage salicylic acid was added as the aromatic monocarboxylic acid in place of tho benzoic acid used in Example No. 1.

That is, to 50 grams of the resinou condensate made as in Example No; 1, I added 154 grams of high-test glycerine, which formed a homogeneous mass with the condensate. Similarly to the procedure of Example No; 1, 148 grams of phthalic anhydride was added and the mixture was heated to about 300 F. until capable of forming a clear head.

Then 76 grams of salicylic acid was added, and heating was continued until the temperature reached about 400 F., at which temperature all the salicylic acid Went into the batch. The batch was cooled.

The product was a solid, viscous, clear, resinous material of particularly pale color. The same uses are indicated for this product as for the product obtained by modification with benzoic acid.

rial formed as above by partial esterification of the condensate in reaction with the phthalic an- Example No.

perature of the reaction mass, or batch, from the maximum temperature of .the' next preceding stage of the process to a temperature slightly above 400 F. At such temperature all of the cinnamic acid quickly went into the batch with the formation of a slight cloud to give when cooled an opaque resinous product of a milky appearance. The exposed surface turned tan in" color.

Example N 0. 6

In this example the procedure and materials of Example No. l were duplicated down to the final stage, in which stage 82 grams of anthranilic acid were used as the monocarboxylic acid in place of the benzoic acid added in Example No. 1. The anthranilic acid was added in small increments while raising the temperature of the reaction mass, or batch, from the maximum temperature of the next preceding stage of the process to a teperature slightly above 400 F. At such temperature all the anthranilic acid qu ckly went into the batch to give when cooled a semi-transparent, semi-solid resinous product of a yelloworange color closely similar to the product obtained in Example No. 5.

Example No, 7

Example No. 8

I mixed 215 grams of commercial phenol approximately l00%) with 165 grams of commercial acetaldehyde (approximately 100%) together with 11 cc. of sodium hydroxide catalyst in a concentration of 250 m lligrams per cc. This mixture was refluxed until the first sign of separation of water occurred. Such separation is indicated by clouding in a cooled sample or region of the reaction mass and may be observed, for instance, in the cool region of the glass reaction fiask forming part of the exper mental or checking apparatus. Upon the appearance of such cloud and cooling the batch. an opaque ma s of resinous condensate is formed together with an appreciable quantity of free water.

Taking grams of the condensate thus formed.

I mixed with it 154 grams of high-test glycerine. forming a homogeneous mass. I then added 148 grams of phthalic anhydride with heating to a temperature of about 300 to drive off the water of reaction as a vapor and to fuse the phthalic anhydride. During this procedure. I was careful that the temperature was not raised substantially above 320 F. pending the next stage of the process.

In effecting modification of the resinous matehydride, heating of the batch was continued and was held until the batch was capable. of forming a clear bead. At that stage and without per mitting the material to gel, I added 73 grams of benzoic acid with heating of the batch from the maximum temperature of the stage next preceding, which is about 300 F., to a temperature of about 400 F. The batch was held at that latter temperature for a short time, and then cooled. The product was a very dark and clear viscous semi-solid resinous material.

* The procedure and materials of Example No. 8

were duplicated down to the final modification,

in which stage I added in one instance salicylic acid and in anotherinstance cinnamic acid. In both cases there is only slight difference in the product from the "product obtained in Example No. 8.

Example No. 9

I mixed 300 grams of formaldehyde (approximately 40%) and 215 grams of phenol (approximately with 11 cc. of sodium hydroxide catalystin a concentration of 250 milligrams per cc. This mixture was refluxed until the first sign of separation of water occurred, Such separation is indicated by clouding in a cooled sample, or region, of the reaction mass; and may be observed for instance in the cooled region of a glass reaction flask forming part of experimental or checking apparatus. Upon the appearance of such cloud, and cooling the batch, an opaque mass of resinous condensate formed, together with an appreciable quantity of free water.

Taking 50 grams of the condensate thus formed I washed it several times with water and removed as much Water as possible by decantation and squeezing, in accordance with my preferred practice. Prior to any additional heating of the condensate, I mixed with it 154 grams of hightest glycerine forming a homogeneous mass. I then added 148 grams of phthalic anhydride and heated the mixture to such temperature (about 300 F.) that the water of reaction came oil as vapor and the phthalic anhydride was fused, taking care that the temperature was not raised substantially above 320 F. pending the next stage of the process.

In effecting modification of the resinous material formed as above by effective esterification of the condensate and reaction with the phthalic anhydride, heating of the batch was continued and held to the formation of a clear bead. At that stage and without permitting the material to el, I added '73 grams of benzoic acid with heating from the maximum temperature of the stage next preceding to a temperature of about 400 F.

The product was in its properties identical with the products similarly produced by successive reactions with a condensate formed from metapara-cresol and formaldehyde, and was lighter in" color than the products made by reactions with a condensate formed from phenol and acetaldehyde. The'process was conducted in exactly the same manner, and the same principles and considerations as in Example No. 1 were obtained.

The procedure and materials of Example No. 9 were duplicated down to the last addition. in which stage I added in one instance salicylic acid,

and in another instance cinnamic acid. In both cases there were only slight difierences in the products so obtained from the product obtained in Example No. 9.

Example No. I,

resinous condensate formed, together with an appreciable quantity of free water. 7

Taking 50 grams of the condensate thus formed,

Upon the appearance 'of such' cloud, and cooling the batch, an opaque mass'of I mixed with it 154 grams of high-test glycerine, 7

forming a homogeneous mass. I thenadded 148 grams of phthalic anhydride and heated the n'iixev ture to such temperature (about 300. F.) that the water of reaction came off as vapor and the phthalic anhydride was fused, taking care that the temperature was not raised substantially above 320 F. pending the next stage of the proc- ESS- In effecting modification of the resinous material formed as above by effective esterification of the condensate and reaction with phthalic anhydride, heating of the'batch was continued and held to the formation of a clear bead. .At

that'stage and without permitting the material to gel, I added 73 grams of benzoic acid with heating from the maximum temperature of the stage preceding to a temperature of about 400F.

The product was in its properties identical with material having by virtue of itsresin content exceptional capacity'to acquire gloss and hardness in a film.

. Example No..13'

TolOO parts by weight of the resinous product obtained from the procedure of ExampleNo. 9,

I added 100 parts by weight of linseed oil, the

temperature of. the resinous product being maintained at about 430 F. While the linseed oil was very slowly added. The product was a coating material having by virtue of its resinous content exceptional capacity to acquire gloss and hardness in a film.

The procedure of Examples Nos. 11, 12, and 13 was duplicated, adding, however, 100 parts by weight of soya bean oil in place of the linseed oil addedin those examples.

- It has been noted that the temperature at which condensation takes place is relatively low, being for example of an order exemplified by reflux conditions such as are typical in making phenol-aldehyde condensates of the infusible Resite or Bakelite type, in distinction from thefusible, 0r Novolak, type condensates. To insure the formation of a condensate of the desired Resite type, I use in the initial condensate a phenol selected from the group of phenols k consisting of meta-para-cresol, phenol, and xylethe product similarly produced by successive reaction with the condensate formed from phenol and. acetaldehyde. The process was conducted in exactly the same manner as in Example No. 1, and the same principles and considerations as in ExampleNo. 1 obtained.

. Paralleling the procedure as described in Examples Nos. 1, 2, and 3, I have made to the partial 'esterification products as produced in Ex- 7 ample No. 10 above given, and invariants of that example in which phthalic anhydride was replaced by maleic acid and fumaric acid, addition of the several monocarboxylic acids the use of which isfldescribed in Examples Nos. 4 to 8 inclusive, thus similarly making addition of sali- "cylic acid, cinnamic acid, anthranilic acid, and

phenyl-acetic acid. The results were consistently similar to those arrived at in Example No. 10, with some variation 'in color, consistency, and clarity of the product.

Example No. 11

To 100 parts by weight of the resinous product made in accordance with Example No. 4, I

7 added 100 parts by weight of linseed oil, the temperature of the resinous product being maintained at about 430 F. while the linseed oil was very slowly added. The product was a coating nol, and do not use the phenolics, such as butylphenol, or para-tertiary amyl-phenol, which tend to give a phenol-aldehydecondensate which is inherently more'fusible and which is incapable of imparting to the final products the properties of. hardness and gloss typical of the infusiblepor R esite, type phenol-aldehyde condensates.

Although I use an initial condensate inherently possessing full heat-hardening properties,

by using. an unmodified polyhydric alcohol, by causing that alcohol to solublize the initial condensate, and without the use of added solubilizing agents, 1' am able to maintain the reaction mass, or batch, in a fusible condition which permits the reaction with the polybasic carboxylic acid appropriately to take place. Also by the avoidance of high temperature in the batch prior to the addition of the'aromatic monocarboxylic acid in the final stage, the batch being still in solubilized condition by virtue of the use of un: modified polyhydric alcohol and the conditions of its use, I am enabled tomake substantial additions of monocarboxylic acids of the sort to which this present invention relates. The quantityt. of such monocarboxylic acids which .are added is not critical, but as'above noted increased quantity tends to increased solubility of the resinous products obtained.

Since in distinction from my previous application, to which reference has been above made, I utilize as the final modifying ingredient of my resin aromatic monocarboxylic acids, I have herein noted and exemplified a relatively great number of 'such monocarboxylic acids. The employment of various polybasic carboxylic acids in making alkyd modification in phenol-aldehyde resins having been fully developed in the art, I have exemplified herein phthalic anhydride, maleic anhydride, malic acid, and fumaric acid. It is to be understood, however, that any other polybasic 'carboxylic acid which the art has found to be suitable for the alkyd modification of phenol-aldehyde resins may be employed while conforming to the principles of my invention, and following the procedure of my method as outlined in the examples given above. I may also give as exemplary of polyhydric alcohols mols. of iormaldehyde,

' other than glycerine, triethylene glycol, diethylene glycol, pentaerythritol, and sorbitol. When used as equivalents for ghrcerine these alcohols are used in quantities of approximate molar equivalency with the glycerine specifically noted I tial esterification product thus formed at least one addition of a monocarboxylic acid selected method is to give a resin suitable for various uses, and particularly adapted for use in elec-' trlcal insulating varnishes and in adhesives in which the initial condensate is a resin of full heat-hardening properties, and in which the advantageous features attendant upon those properties are retained, by so including the polyhydric alcohol and the polybasic carboxylic acid in the batch by which the resin is formed that I am able to obtain the desired sequence of reactions without the addition of anysolubilizing agent, such as a resin, or by the addition of a solubllizing acid, such as a monocarboxylic acid prior to the reaction with polybasic carboxylic acid. The product resins thus retain hardness, gloss, and alkali resistance characteristic of molding resins of the full heat-hardening type, in resins suitable for use in adhesives and coatings. In these resins, also, the character of the monocarboxylic acid included as a modifying addition in the process of their manufacture gives the resins effective solubility in a wide range of commercial solvents;

I claim as my invention:

1. The herein described method of producing a modified phenol-aldehyde resin by the sequential steps of forming an initial phenol-aldehyde condensate of the infusible type by refluxing aldehyde with a phenol selected from the group consisting of metapara-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols. of aldehyde to 1 mol. of the phenolto the stage at which water separates on cooling, forming a homogeneous mass of the condensate and an unmodified polyhydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive off water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of a solubilizing agent and holding to a clear bead, in the reaction mass the polyhydric alcohol being in excess acid and both being in excess of the initial condensate, and with heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of a monocarboxylic acid selected from the class consisting of the aromatic monocarboxylic acids, and mixtures of such acids.

2. The herein described method of producing a modified phenol-formaldehyde resin by the sequential steps of forming an initial phenolformaldehyde condensate of the infusible type by refluxing formaldehyde with a phenol selected from the group consisting of meta-para-cresol,

phenol, and xylenol in the presence of an alkaline proportion of at least 1.5

catalyst in the reacting to 1 mol. of the phenol to of the polybasic carboxylic forming a homogeneous mass of the condensate and an unmodified polyhydric alcohol, and reacting the said mass with a polybasic carboxylic acid with heating to a'temperature adequate to drive of! water and to fuse the polybasic carboxylic acid and not substantially exceeding 320F. in the absence of a solubilizing agent and holding to a clear head, in the reaction mass the polyhydric alcohol being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with further heating to a temperature of about 400 F. making to the parfrom the class consisting of the aromatic monocarboxylic acids and mixtures of such acids.

3. The herein'described method of producing a modified phenol-aldehyde resin by the sequential steps of forming an initial phenol-aldehyde condensate of the infusible type by refluxing aldehyde with a phenol selected from thegroup consisting of meta-para-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5-mo1s. of aldehyde to 1 mol. of the'phenol to the stage at which water separates on cooling, forming ahomogeneous mass of the condensate and an unmodified ,polyhydric alcohol. and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive ofl water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of a solubilizing agent and holding to a clear bead, in the reaction mass the polyhydric acid being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with heating to a temperature of about 400 F. making to the partial esterification product thus 40 formed at least one addition of benzoic acid.

4. The herein described method of producing a modified phenol-formaldehyde resin by the sequential steps of forming an initial phenolformaldehyde condensate of the infusible type by refluxing formaldehyde with a phenol selected from the group consisting of meta-para-cresol,

phenol, and xylenol, in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols. of formaldehyde to 1 mol. of the phenol to a stage at which water separates on coolin forming an homogeneous mass of the condensate and an unmodified polyhydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive ofl water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in

the absence of a solubilizing agent and holding to a clear bead, in the reaction mass the polyhydric alcohol being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with further heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of benzoic acid.

5. The herein described method of producing a modified phenol-aldehyde resin by the sequential steps of forming an initial phenol-aldehyde condensate of the iniusible type by refluxing aldehyde with a phenol selected from the group consistlng of meta-para-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols. of aldehyde to 1 mol. of the phenol to the stage at which water separates on cooling, forming a homogeneous mass of the condensate and an unmodified polya stage at which water separates on cooling,

hydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive oil water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of asolubilizing agent and holding to a clear bead, in the reaction mass the polyhydric acid being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of salicylic acid.

6. The herein described method of producing a modified phenol-formaldehyde resin by the sequential steps of forming an initial phenol-formaldehyde 'condensate of the infusible type by refluxing formaldehyde with a phenol selected from the group consisting of meta-para-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols.

of formaldehyde to 1 mol. of the phenol to a stage at which water separates on cooling, forming a homogeneous mass of the condensate and an unmodified polyhydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive oif water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of a solubilizing agent and holding to a clear head,

in the reaction mass the polyhydric alcohol being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with further heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of salicylic acid.

7. The herein described method of producing a modified phenol-aldehyde resin by the sequential steps of forming an initial phenol-aldehyde condensate of the infusible type by refluxing aldehyde with a phenol selected from the group consisting of meta-para-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols. of aldehyde to 1 mol. of the phenol to the stage at which water separates on cooling, forming a homogeneous mass of the condensate and an unmodified polyhydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive off water and to fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of a solubilizing agent and holding to a clear bead, in the reaction mass the polyhydric acid being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of anthranilic acid.

8. The herein described method of producing a modified phenol-formaldehyde resin by the sequential steps of forming an initial phenol-formaldehyde condensate of the infusible type by refluxing formaldehyde with a phenol selected from the group consisting of meta-para-cresol, phenol, and xylenol in the presence of an alkaline catalyst in the reacting proportion of at least 1.5 mols. of formaldehyde to 1 mol. of the phenol to a stage at which water separates on cooling, forming a homogeneous mass of the condensate and an umnodified polyhydric alcohol and reacting the said mass with a polybasic carboxylic acid with heating to a temperature adequate to drive off water and to. fuse the polybasic carboxylic acid and not substantially exceeding 320 F. in the absence of a solubilizing agent and holding to a clear bead, in the reaction mass the polyhydric alcohol being in excess of the polybasic carboxylic acid and both being in excess of the initial condensate, and with further heating to a temperature of about 400 F. making to the partial esterification product thus formed at least one addition of anthranilic acid.

- SAMUEL S. GUTKIN. 

